Rate constants for the gas-phase reactions of OH and NO3 radicals and O3 with sabinene and camphene at 296±2 K

The rate constants for the gas-phase reactions of sabinene and camphene, two monoterpenes emitted from vegetation, with OH and NO₃ radicals and O₃ have been determined at 296±2 K and one atmosphere total pressure of air. The OH and NO₃ radical reaction rate constants were determined using relative rate techniques. Using rate constants of k(OH + isoprene) = 1.01 × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, k(NO₃ + trans-2-butene) = 3.87 × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ and k(NO₃ + 2-methyl-2-butene) = 9.33 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, the following OH and NO₃ radical reaction rate constants (in cm³ molecule⁻¹ s⁻¹ were obtained: OH radical reaction; sabinene, 1.17 × 10⁻¹⁰ and camphene, 5.33 × 10⁻¹¹; NO₃ radical reaction; sabinene, 1.01 × 10⁻¹¹, and camphene, 6.54 × 10⁻¹³. The absolute O₃ reaction rate constants determined were (in cm³ molecule⁻¹ s⁻¹ units): sabinene, 8.07 × 10⁻¹⁷, and camphene, 9.0 × 10⁻¹⁹. These rate constants are compared to literature data for other structural-related alkenes and monoterpenes.     

Decomposition of CF3CI by corona discharge

In this paper pulsed corona discharge is shown to be effective for the decomposition of CF₃Cl(Freon-13).The pressure of CF₃Cl was 2.67×10³Pa,after discharged for 2 min,39.5% of CF₃Cl was decomposed.The products were mainly CF₄,Cl₂ and CF₂Cl₂.The yield increased by adding O₂ or air.Under the same conditions,more than 94% decomposition yield was obtained if 5.32×10³Pa O₂ or air was added.The composition of products became CF₂O,Cl₂ and CF₄.While the partial pressure of O₂ or air reached 1 arm,the decomposition yield decreased to 54.5% and 48. 5% respectively.     

Polynuclear aromatic hydrocarbon degradation by heterogeneous reactions with N2O5 on atmospheric particles

The degradation of particulate polynuclear aromatic hydrocarbons (PAH) on atmospheric soot particles in the presence of gas phase dinitrogen pentoxide (N₂O₅) was explored. Dilute diesel and wood soot particles containing PAH were reacted with∼10ppm of N₂O₅ in a 200 ℓ continuous stirred tank reactor (CSTR). To provide a stable source of particles for reaction in the CSTR, diesel or wood soot particles were injected at night into a 25 m³ Teflon outdoor chamber. The large chamber served as a reservoir for the feed aerosol, and the aerosol could then be introduced at a constant flow rate into the CSTR. PAH-N₂O₅ heterogeneous rate constants for wood soot at 15°C ranged from2 × 10⁻¹⁸to5 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. For diesel soot the rate constants at 16°C were higher and ranged from5 × 10⁻¹⁸to30 × 10⁻¹⁸ cm³ molecules⁻¹ s⁻¹. Comparisons with other studies suggest that sunlight is the most important factor which influences PAH decay. This is followed by ozone, NO₂, N₂O₅ and nitric acid. The rate constants of nitro-PAH formation from a parent PAH and N₂O₅ were of the order of1 × 10⁻¹⁹−1 × 10⁻¹⁸ molecules⁻¹s⁻¹. The uncertainty associated with all of these rate constants is± a factor of 3. Given, however, the small magnitude of the rate constants and the low levels of N₂O₅ present in the atmosphere, we concluded that PAH heterogeneous reactions with gas phase N₂O₅ degrade particle-bound PAH or to form nitro-PAH from PAH arenot very important. (Direct application of the specific rate constants derived in this study to ambient atmospheres should not be undertaken unless the ambient particle size distributions and chemical composition of the particles are similar to the ones reported in this study.)     

ECD氧气诱导法分析大气中痕量HCFC-22

HCFC-22(CHClF₂)是CFC-12的主要替代物,它在大气中的体积分数仅为10^-12级.而且对ECD检测器响应灵敏度很低.本文经过低温浓缩进样后采用氧气诱导法来增强ECD对它的分析灵敏度,载气中氧气的体积分数为0.54%时,信噪比最大,此时ECD灵敏度增强约500倍.结合该条件下ECD温度选择、程序升温和载气流量的研究,建立了高灵敏度ECD气相色谱测定大气中HCFC-22浓度的实用分析方法.     

CF2ClBr的火花等离子体降解

对用等离子体降解ＣＦ２ＣｌＢｒ进行了初步研究,产物主要用气相色谱分析。在ＣＦ２ＣｌＢｒ的强为２．６７×１０＾３Ｐａ时获得了９０％左右的解离率,主要降解产为ＣＦ３Ｃｌ,Ｂｒ２,ＣＦ４,ＣＦ２Ｃｌ２。另外,从热力学上对产物进行了解释,得出了产总是朝使体系更稳定的方向生成的结论。     

GC-MS和GC-ECD同时在线观测本底大气中的HCFC-142b

2010年5月～2011年5月,利用自组装气相色谱-质谱联用法(GC-MS)和气相色谱-电子捕获检测法(GC-ECD)在线观测系统,在北京上甸子区域大气本底站开展了二氟一氯乙烷(HCFC-142b)在线观测对比实验,GC-MS和GC-ECD系统分析精度分别为0.23%和0.88%.观测期间HCFC-142b浓度变化范围约为21×10-12～355×10-12;通过独立样本T检验P>0.05,表明两种方法获得的HCFC-142b浓度数据无显著性差异;对两套系统观测浓度数据的差值分析表明,造成两套系统观测浓度间微小差别的主要因素是空气样品时间分辨率和观测精度.利用局部近似回归法进行本底值筛分,GC-MS和GC-ECD法获得的本底浓度均值差、中值差、25和75百分位数值差均优于系统观测精度.两种方法捕获HCFC-142b污染过程一致,污染浓度均具有夏秋高冬低的特点;两种方法观测HCFC-142b污染浓度的年变化趋势一致.     

Heterogeneous transformation of peroxyacetylnitrate

The heterogeneous decomposition of peroxyacetylnitrate (PAN) has been investigated using a flow reactor and infrared spectroscopic analysis. The decomposition rate in air due to glass surfaces follows the relation d[PAN]/dt = −S/V([PAN] × 7 × 10⁷ + [CH₃C(O)OO] × 5 × 90¹²)exp(−9382/T) molecules cm⁻³ s⁻¹ (S/V=surface to volume ratio). The rate observed for NH₄HSO₄-covered surfaces is lower than in the glass case. The rate is high enough to affect many laboratory experiments but too slow to have any influence on PAN decomposition under ambient conditions.     

Field studies of the SO2/aqueous S(IV) equilibrium in clouds

Concentrations of S(IV) were measured in cloudwater at Great Dun Fell and compared with theoretical HSO₃⁻ assuming equilibrium between aqueous and gaseous phases in cloud. Detectable concentrations of S(IV) in the range of 1 × 10⁻⁶ to 17.2 × 10⁻⁶ mol dm⁻³ were observed only in samples which contained low H₂O₂ concentrations, generally <1 × 10⁻⁶ mol dm⁻³. Concentrations of S(IV) were below the detection limit of 1 × 10⁻⁶ mol dm⁻³ in samples which contained hign H₂O₂ levels (1 × 10⁻⁶−80 × 10⁻⁶ mol dm⁻³) confirming that either SO₂ or H₂O₂ acts as the limiting reagent in the oxidation of SO₂ in cloudwater.Equilibrium HSO₃⁻ concentrations were estimated from the measured cloudwater pH, the gas phase SO₂ concentration and the ambient temperature and found to be on average about 5 times lower than the measured S(IV) concentrations. The possible role of formaldehyde in stabilizing S(IV) in cloudwater is discussed. The kinetic data available in the literature suggest that the complexation reaction between S(IV) and HCHO is too slow to account for the observed difference between measured and calculated S(IV) concentrations over the typical lifetime of clouds in our study.S(IV) accounted for up to 10% of the SO₄²⁻ measured in stored cloudwater samples.     

Precision of the radiochemical OH measurement method

Twenty-eight radiochemical ¹⁴C tracer measurement of tropospheric hydroxyl radical (OH) concentrations were obtained at a rural site near Washington State University, Pullman, WA (117°W, 47°N). Diurnal OH concentration variations were observed for the five days between 9 August and 14 August 1990. These data made it possible to estimate the midday precision and detection limit of the radiochemical OH measurement method. Experiments performed at a peak O₃ photolysis rate J (O(¹D)) of (3.0±0.2) × 10⁻⁵ s⁻¹ yielded a mean midday OH concentration of (5.6±0.1 (1σ)) × 10⁶ cm⁻³. Other data put an upper bound of 16% on fluctuations of instrument sensitivity. Low-light or nighttime background OH concentrations were less than (2.6±2) × 10⁵ cm⁻³. A lower detection limit of 10⁵ cm⁻³ was obtained when extra care was taken with the low-level ¹⁴C counting procedure.     

The role of copper and oxalate in the redox cycling of iron in atmospheric waters

During daytime, the redox cycling of dissolved iron compounds in atmospheric waters, and the related in-cloud transformations of photooxidants, are affected by reactions of Fe and Cu with hydroperoxy (HO₂) and superoxide (O₂⁻) radicals and the photoreduction of Fe(III)-oxalato complexes. We have investigated several of the important chemical reactions in this redox cycle, through laboratory simulation of the system, using γ-radiation to produce HO₂/O₂⁻. At concentrations comparable to those measured in atmospheric waters, the redox cycling of Fe was dramatically affected by the presence of oxalate and trace concentrations of Cu. At concentrations more than a hundred times lower than Fe, Cu consumed most of the HO₂/O₂⁻, and cycled between the Cu(II) and Cu(I) forms. Cu⁺ reacted with FeOH²⁺ to produce Fe(II) and Cu(II), with a second order rate constant of approximately 3 × 10⁷ M⁻¹s⁻¹. The presence of oxalate resulted in the formation of Fe(III)-oxalato complexes that were essentially unreactive with HO₂/O₂⁻. Only at high oxalate concentrations was the Fe(II)C₂O₄ complex also formed, and it reacted relatively rapidly with hydrogen peroxide (k = (3.1 ± 0.6) × 10⁴ M⁻¹s⁻¹). Simulations incorporating measurements for other redox mechanisms, including oxidation by ozone, indicate that, during daytime, Fe should be found mostly in the ferrous oxidation state, and that reactions of FeOH²⁺ with Cu(I) and HO₂/O₂⁻, and to a lesser degree, the photolysis of Fe(III)-oxalato complexes, are important mechanisms of Fe reduction in atmospheric waters. The catalytic effect of Cu(II)/Cu(I) and Fe(III)/Fe(II) should also significantly increase the sink function of the atmospheric liquid phase for HO₂ present in a cloud. A simple kinetic model for the reactions of Fe, Cu and HO₂/O₂⁻, accurately predicted the changes in Fe oxidation states that occurred when authentic fogwater samples were exposed to HO₂/O₂⁻.     

Real-time,in situ measurements of atmospheric optical absorption in the visible via photoacoustic spectroscopy—IV. Visibility degradation and aerosol optical properties in Los Angeles

Aerosol light absorption (b_abs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol b_abs (λ = 514.5 nm) varied from an hourly average value of 7 × 10⁻⁶ m⁻¹ in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10⁻⁵ m⁻¹ in the 7–8 a.m. period of both 28 August and 3 September. This b_abs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.     

海峡西岸经济区大气污染物排放清单的初步估算

以2009年为基准年,结合污染源普查数据、统计年鉴及工业活动、居民生活等多个方面对海峡西岸经济区包括SO2、NOx、PM2.5、VOCs和NH3在内的大气污染物的排放量进行了估算,建立了海西区大气污染物排放清单.结果发现,上述5类污染物基准年的排放量分别为40.67×104、55.84×104、50.57×104、152.26×104和26.18×104t.其中,SO2、NOx及PM2.5的排放主要来自电厂,占排放总量的比例分别为25.58%、34.89%和38.75%;VOCs和NH3的主要排放源分别来自植被排放和养殖业,其贡献量分别为49.12%和47.07%.采用GIS对排放清单进行网格化处理,得出SO2、NOx及PM2.5的高排放强度区域与固定源的空间分布较为一致.此外,结合国家和地方"十二五"发展规划,采用情景分析方法估算了2015年海西区大气污染物的排放清单.与基准年相比,SO2、NOx和NH3的排放量呈下降趋势,PM2.5和VOCs的排放量呈大幅度增加.基准年排放清单的不确定性分析显示,VOCs排放估算的不确定度最大,为225%.     

Wintertime measurements of aerosol acidity and trace elements in Wuhan,a city in central China

A 2-week intensive ambient aerosol study was conducted in December 1988 in Wuhan (Hubei Province), a city of nearly 2 million located on the Yangtze River in central China (P.R.C.). This is an industrial region where soft coal burning is widespread, and emission controls for vehicles and industrial facilities are minimal. The sampling site was located in one of the civic centers where residential and commercial density is highest. An Andersen dichotomous sampler was operated with Teflon membrane filters to collect fine (d_p < 2.5 μmad) and coarse (2.5 ⩽ d_p < 10 μmad) particles for total mass and element determinations. An annular denuder system (ADS) was used to collect fine fraction aerosols for analyses of ionic species including strong acidity (H⁺).The study was conducted between 18 and 30 December, which was rainless, consistently cool (3–10°C) and overcast, but without fog or acute stagnation. Fine particulate mass (PM, as μ m⁻³) averaged 139 (range 54–207); coarse PM averaged 86 (range 29–179). Trace element concentrations were also high. Crustal elements (Si, Al, Ca and Fe) were found primarily in the coarse fraction, while elements associated with combustion (S, K, Cl, Zn and Se) were enriched in the fine fraction. The concentrations of arsenic and selenium were evidence of a large source of coal burning, while vanadium levels (associated with fuel oil use) were not especially enriched.Despite the seemingly high PM loadings, ionic concentrations were not especially high. The average composition of soluble fine aerosol species (in neq m⁻³) were SO₄²⁻: 520 (range 180–980), NO₃⁻: 225 (range 50–470), Cl⁻: 215 (range 20–640), and NH₄⁺: 760 (range 280–1660). A deficit in accountable FP components (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³. (total mass compared to the total of ionic plus element masses) as well as the black appearance of collected materials indicate an abundance of carbonaceous aerosol, as high as 100 μ m⁻³Aerosol acidity was negligible during most monitoring periods, H⁺: 14 (range 0–50 neq m⁻³, equivalent to 0–2.5 μm m⁻³ as H₂SO₄). Sulfur dioxide, measured by the West-Gaeke method for part of the study, concentrations were low. Although not directly measured, the aerosol measurments suggested that gaseous HCl (from refuse incineration) and NH₃ (animal wastes) concentrations might have been high. Higher aerosol acidity might be expected if HCl sources were more prominent and not neutralized by local ammonia or other base components.     

廊坊市区主要大气污染源排放清单的建立

通过调研、统计廊坊市区工业、城中村及机动车等资料,结合以往清单文献研究结果及清单编制指南中的排放因子,计算了廊坊市区主要大气污染物的排放量,得到廊坊市区2014年主要大气污染源排放清单.结果显示,2014年廊坊市区工业源(固定燃烧)NO_x、SO_2、NMVOC、CO、PM_(10)、PM_(2.5)排放总量分别为6.4×10~3、1.2×10~4、31、1.0×10~4、7.3×10~2、4.4×10~2t,其中热电行业排污贡献率最高,分别占NO_x、SO_2、CO、PM_(10)、PM_(2.5)工业源(固定燃烧)年排放总量的55%、48%、67%、63%、69%;安次区工业企业对气态污染物贡献较高,广阳区及开发区工业企业对颗粒物排污贡献较大.低矮面源(城中村)NO_x、SO_2、NMVOC、CO、PM10、PM_(2.5)年排放总量分别为1.8×10~2、3.6×10~3、3.0、4.9×10~3、1.5×10~2、72 t.道路移动源CO、HC、NO_x、PM_(2.5)年排放总量分别为2.4×10~4、1.9×10~3、2.2×10~3、44 t,其中小型客车对HC和CO贡献率较高,分别为53%和61%;NO_x年排放总量中26%由重型货车贡献;PM_(2.5)则主要由轻型货车和重型货车贡献,占比分别为39%和21%.     

CF2ClBr在短紫外光照射下光解离过程的研究

以低压汞为激发光源,气相色谱和红外光谱为主要分析手段,研究了气态ＣＦ２ＣｌＢｒ在１８５ｎｍ紫外光照射下的光解离过程及其人在Ｏ２存在下的光氧化机理,发现ＣＦ２ＣｌＢｒ在１８５ｎｍ紫外光照射下的主要产物ＣＦ２Ｂｒ２ＣＦ２Ｃｌ２和Ｃｌ２,Ｂｒ２,而当Ｏ２存在时,主要光解产物为ＣＦ２Ｏ,在本实验条件下,纯ＣＦ２ＣｌＢｒ极限分解率约为２６％,在ＣＦ２ＣｌＢｒ－Ｏ２体系中,ＣＦ２ＣｌＢｒ的解离为一级反应,速率     

CH4 emission model from the waste of Sus Domesticus and Gallus Domesticus in Nigerian local farms: environmental implications and prospects

The potential of CH₄ (methane) greenhouse gas (GHG) emissions based on a model of prevailing behavioural pattern of livestock waste management in Nigerian local farms was investigated in this paper. Livestock waste, from Sus domesticus, pig, and Gallus domesticus, poultry, were employed as substrates in the study which uses water from a fish rearing farm as the matrix medium to simulate wastewater pool/river environment. A substrate to fish-water ratio of 1:3 by mass was used in developed laboratory-size digesting reactor system with U-tube water displacement, to facilitate volumetric readings of gas production, for each mix of the livestock waste. Volumetric readings from these, at ambient temperature conditions in the retention time of 32 days, follow the Normal probability density function, in accordance with Kolmogorov-Smirnov goodness-of-fit criteria. These readings showed that CH₄-containing gas as high as 67.3?×?10^?3 dm³ was produced on the 14th day from the pig and 86.8?×?10^?3 dm³ on the 13th day from the poultry substrates. The overall CH₄-containing gas productions of 255.4?×?10^?3 dm³/kg and 323.58?×?10^?3 dm³/kg were observed for the pig and the poultry substrates, respectively. A 70% scale-up analysis, modelled from these results, for the nation yield potential emission of about 4 kg CH₄ (that could be as potent as 84 kg CO₂-equivalent) annually. The environmental implications on global warming and possible prospects of recoverable domestic benefits from the waste through the adoption of sustainable policy of livestock waste managements for mitigating the CH₄ emissions in Nigerian local farms are presented.     

Studies on the formation of H2O2 in the ozonolysis of alkenes

The formation of H₂O₂ in the reactions of ozone with alkenes, isoprene and some terpenes has been studied with tunable diode laser absorption spectroscopy. The measured yields of H₂O₂ were found to be considerably enhanced in the presence of water vapour. H₂O₂ is thought to be formed in the ozonolysis of the alkene with O₃ by direct reaction of an intermediate with water vapour. The yield of H₂O₂ relative to the reacted alkene in the ozonolysis of trans-2-butene in the presence of water vapour was also studied with long path FTIR spectroscopy. Irrespective of the analytical methods and reaction conditions applied, the H₂O₂ yields in the reaction of O₃ with the different alkenes in the presence of water vapour were found to be in the range of a few per cent or less. Under the assumption that the reactive species forming H₂O₂ in the ozonolysis is the Criegee biradical, the overall rate constants for the reactions of some biradicals with water vapour were measured relative to the rate constant of the biradical with SO₂. For the H₂COO biradical a rate constant of (5.8 ± 2.5) × 10⁻¹⁷ cm³ s⁻¹ was determined and for the (CH₃)₂COO biradical (2.9 ± 1.5) × 10⁻¹⁷ cm³ s⁻¹; in the latter case with the assumption that (CH₃)₂COO reacts with SO₂ as fast as CH₂COO.     

Three-wavelength nephelometer suitable for aircraft measurement of background aerosol scattering coefficient

A new nephelometer suitable for aircraft measurements of aerosol scattering extinction coefficient (σ_sp) has been constructed and operated under field conditions. This instrument is vacuum tight for operation in a pressurized aircraft cabin and is capable of measuring background tropospheric σ_sp at an averaging time of 1 min. For example, in a typical atmospheric profile the instrument can measure values of about 10⁻⁴ m⁻¹ with a time resolution of 2 s in a polluted region, and about 10⁻⁷ m⁻¹ with a time resolution of 1 min in a clean region. This sensitivity is made possible by: (1) subtracting in real time the air Rayleigh scattering from the total scattering signal by continuously measuring pressure and temperature in the sampling volume of the instrument; (2) correcting for the dark count and sensitivity of the photomultipliers using a rotating shutter; and (3) using a beam splitter arrangement to allow simultaneous detection by three photomultipliers. A laboratory measurement of instrument noise suggests a 550-nm noise level of about 5 × 10⁻⁸ m⁻¹ at an averaging time of 1 min.     

Southern California air quality study: A search for methyl nitrate

Methyl nitrate, CH₃ONO₂, was measured by electron capture gas chromatography (EC-GC) under conditions which allowed resolution of methyl nitrate, PAN, and several chlorinated hydrocarbons. Calibrations involved both EC-GC andNO_x chemiluminescence and were in agreement with independent calibrations involving i.r. spectroscopy. The rate constant for photolysis of methyl nitrate in sunlight was< 2.3 × 10⁻⁶s⁻¹. Detection limits of field instruments were 0.1–0.4 ppb. Some 3000 EC-GC chromatograms grams of ambient air recorded between June and December 1987, during the Southern California Air Quality Study (SCAQS) at up to nine Southern California locations yielded only seven possible, but unlikely observations of methyl nitrate. Thus, methyl nitrate was only a minor component among nitrogenous air pollutants during SCAQS. The measured CH₃ONO₂/PAN ratios of<0.003–0.2 during SCAQS are discussed in terms of available kinetic data for PAN unimolecular decomposition (a major source of methyl nitrate), PAN thermal decomposition and CH₃ONO₂ photolysis.     

Factors affecting airborne monocyclic aromatic hydrocarbon uptake by plants

Three factors influencing foliar uptake of monocyclic aromatic hydrocarbons (MAHs; benzene, toluene, ethylbenzene, xylenes) in situ were investigated. The first factor, the plant species, was found to determine absorption pattern and concentrations. Secondly, time variation studies showed that response of leaf concentrations to small changes in air concentrations only occurs after several days or weeks, whereas adaptation to a much higher level of air pollution takes several months. Thirdly, MAH leaf concentrations were observed to be dependent on mean air pollution at the sampling site. Bioconcentration factors BCF_vs (g m⁻³ of wet leaf/g m⁻³ of air) for MAHs in Pseudotsuga menziesii (Mirb.) Franco leaves were determined to range from 2.7 × 10⁴ to 4.7 × 10⁵.